The kinetics of NO and N2O reduction over coal chars in fluidised-bed combustion

This paper presents a comprehensive and critical review of the mechanisms and kinetics of NO and N2O reduction reaction with coal chars under fluidised-bed combustion conditions (FBC). The heterogeneous reactions of NO and N2O with char/carbon surface have been well recognised as the most important processes in reducing both NOx and N2O in situ FBC. Compared to NO-carbon reactions in FBC, the reactions of N2O with chars have been relatively less understood and studied. Beginning with the overall reaction schemes for both NO and N2O reduction, the paper extensively discusses the reaction mechanisms including the effects of active surface sites. Generally, NO- and N2O-carbon reactions follow a series of step reactions. However, questions remain concerning the role of adsorbed phases of NO and N2O, and the behaviour of different surface sites. Important kinetics factors such as the rate expressions, kinetics parameters as well as the effects of surface area and pore structure are discussed in detail. The main factors influencing the reduction of NO and N2O in FBC conditions are the chemical and physical properties of chars, and the operating parameters of FBC such as temperature, presence of CO, O-2 and pressure. It is shown that under similar conditions, N2O is more readily reduced on the char surface than NO. Temperature was found to be a very important parameter in both NO and N2O reduction. It is generally agreed that both NO- and N2O-carbon reactions follow first-order reaction kinetics with respect to the NO and N2O concentrations. The kinetic parameters for NO and N2O reduction largely depend on the pore structure of chars. The correlation between the char surface area and the reactivities of NO/N2O-char reactions is considered to be of great importance to the determination of the reaction kinetics. The rate of NO reduction by chars is strongly enhanced by the presence of CO and O-2, but these species may not have significant effects on the rate of N2O reduction. However, the presence of these gases in FBC presents difficulties in the study of kinetics since CO cannot be easily eliminated from the carbon surface. In N2O reduction reactions, ash in chars is found to have significant catalytic effects, which must be accounted for in the kinetic models and data evaluation. (C) 1997 Elsevier Science Ltd.

A comparative study of N2O conversion to N-2 over Co/AC and Cu/AC catalysts

Catalytic conversion of N2O to N-2 over Cu- and Co-impregnated activated carbon catalysts (Cu/AC and Co/AC) was investigated. Catalytic activity measurements were carried out in a fixed-bed flow reactor at atmospheric pressure. The catalysts were characterized by N-2 adsorption, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). This study aimed to provide insights into the following aspects: the metal dispersion, changes in pore structure, influence of catalyst loading on reaction, and reaction mechanism. Increasing loading of Co or Cu led to decreasing dispersion, but 20 wt % loading was an upper limit for optimal activities in both cases, with too high loading causing sintering of metal. Co exhibited a relatively better dispersion than Cu. Impregnation of metal led to a large decrease in surface area and pore volume, especially for 30 wt % of loading. 20 wt % of loading has proved to be the optimum for both Cu and Co, which shows the highest activity. Both N2O-Co/AC and -Cu/AC reactions are based upon a redox mechanism, but the former is limited by the oxygen transfer from catalysts to carbon, while N2O chemisorption on the surface of Cu catalyst controls the latter. The removal of oxygen from cobalt promotes the activity of Co/AC, but it is beneficial for Cu/AC to keep plenty of oxygen to maintain the intermediate oxidation of copper-Cu1+. The different nature of the two catalysts and their catalytic reaction mechanisms are closely related to their different electronegativities.

Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

The role of carbon surface chemistry in N2O conversion to N2 over Ni catalyst supported on activated carbon

The effect of acidic treatments on N2O reduction over Ni catalysts supported on activated carbon was systematically studied. The catalysts were characterized by N-2 adsorption, mass titration, temperature-programmed desorption (TPD), and X-ray photoelectron spectrometry (XPS). It is found that surface chemistry plays an important role in N2O-carbon reaction catalyzed by Ni catalyst. HNO3 treatment produces more active acidic surface groups such as carboxyl and lactone, resulting in a more uniform catalyst dispersion and higher catalytic activity. However, HCl treatment decreases active acidic groups and increases the inactive groups, playing an opposite role in the catalyst dispersion and catalytic activity. A thorough discussion of the mechanism of the N2O catalytic reduction is made based upon results from isothermal reactions, temperature-programmed reactions (TPR) and characterization of catalysts. The effect of acidic treatment on pore structure is also discussed. (C) 1999 Elsevier Science B.V. All rights reserved.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

A new CuZ active form in the catalytic reduction of N2O by nitrous oxide reductase from Pseudomonas nautica

J Biol Inorg Chem (2010) 15:967–976 DOI 10.1007/s00775-010-0658-6

Activation of N2O reduction by the fully reduced micro4-sulfide bridged tetranuclear Cu Z cluster in nitrous oxide reductase

J. Am. Chem. Soc., 2003, 125 (51), pp 15708–15709 DOI: 10.1021/ja038344n

Спектры поглошения атмосферных парниковых газов (CH4, N2O, CO)

მოყვანილია ატმოსფეროში არსებული სითბური გაზების შთანთქმის სპექტრების ექსპერიმენტული მონაცემები, მზის რადიაციის ატმოსფეროს ვერტიკალურ სვეტში გავლისას. დადგენილია მზის ინფრაწითელი გამოსხივების სიხშირეთა (Δγ) ინტერვალები, რომლებიც შეესაბამება შესასწავლი გზების შთანთქმის სპექტრებს.

Validation of an analytical method for nitrous oxide (N2O) laughing gas by headspace gas chromatography coupled to mass spectrometry (HS-GC-MS): Forensic application to a lethal intoxication.

Drug abuse is a widespread problem affecting both teenagers and adults. Nitrous oxide is becoming increasingly popular as an inhalation drug, causing harmful neurological and hematological effects. Some gas chromatography-mass spectrometry (GC-MS) methods for nitrous oxide measurement have been previously described. The main drawbacks of these methods include a lack of sensitivity for forensic applications; including an inability to quantitatively determine the concentration of gas present. The following study provides a validated method using HS-GC-MS which incorporates hydrogen sulfide as a suitable internal standard allowing the quantification of nitrous oxide. Upon analysis, sample and internal standard have similar retention times and are eluted quickly from the molecular sieve 5Å PLOT capillary column and the Porabond Q column therefore providing rapid data collection whilst preserving well defined peaks. After validation, the method has been applied to a real case of N2O intoxication indicating concentrations in a mono-intoxication.

Disponibilidade de nitrogênio e fluxos de N2O a partir de solo sob pastagem após aplicação de herbicida

O óxido nitroso (N2O) é um importante gás do efeito estufa, com um alto potencial de provocar o aquecimento global e de vida longa na atmosfera. Grande parte dos fluxos naturais de N2O ocorre a partir dos oceanos, enquanto o restante é resultado principalmente da contribuição de processos microbiológicos (nitrificação e desnitrificação) ocorridos em solos de regiões tropicais. A disponibilidade de N para processos metabólicos dos microrganismos pode ser um importante fator no controle das emissões de N2O nesses solos. O presente trabalho foi realizado com o objetivo de melhorar a compreensão acerca dos controles sobre os fluxos de N2O a partir de solos com pastagem na Amazônia. Foram investigados os efeitos da disponibilidade de N, C e umidade na emissão de N2O a partir do solo de uma pastagem submetida ou não a práticas para recuperação de sua produtividade. O estudo foi realizado em condições de laboratório, incubando o solo coletado nas seguintes situações: (a) Controle - solo com pastagem estabelecida em 1983 e com manejo tradicional, constituída de uma mistura de Brachiaria brinzantha e Panicum maximum, além da presença de uma variedade de plantas invasoras, e (b) Herbicida - dessecação total das plantas da pastagem estabelecida em 1983, para o plantio direto de arroz e posterior ressemeadura de braquiária. É oportuno ressaltar que as amostras de solo (camada de 0-5 cm) das áreas foram coletadas no terceiro dia após a aplicação do agroquímico. Para o estabelecimento das comparações e compreensão dos controles nos fluxos de N2O do solo, foram adicionados ao solo para incubação: nitrato, dextrose e água; além do uso de acetileno para bloquear a oxidação do N2O a N2, estimando, assim, a proporção de N2 que foi emitido do solo. Os maiores fluxos foram observados quando o nitrato foi acrescentado ao solo sob condições de alta umidade. A adição de dextrose (fonte de C) elevou os fluxos de forma mais intensa no solo que recebeu aplicação de herbicida, cuja disponibilidade de N também era maior. Com a aplicação de acetileno foi possível observar que grande parte do N perdido sob formas gasosas ocorre como N2. Desse modo, o processo de desnitrificação mostrou-se dominante nos fluxos de N2O a partir do solo da pastagem estudada, enquanto o N foi o fator principal no controle desses fluxos.

Rotação de culturas no sistema plantio direto em Tibagi (PR): II - Emissões de CO2 e N2O

A atividade agrícola pode alterar a quantidade e qualidade da matéria orgânica do solo (MOS), resultando em emissões de dióxido de carbono (CO2) e óxido nitroso (N2O) do solo para a atmosfera. O sistema plantio direto (SPD) com a utilização de leguminosas em sistemas de rotação é uma estratégia que deve ser considerada tanto para o aumento da quantidade de MOS como para seu efeito na redução das emissões dos gases de efeito estufa. Com o objetivo de determinar os fluxos de gases do efeito estufa (CO2 e N2O) do solo, um experimento foi instalado em Tibagi (PR), em um Latossolo Vermelho distroférrico textura argilosa. Os tratamentos, dispostos em faixas não casualizadas com parcelas subdivididas, foram: sistema plantio direto por 12 anos com sucessões milho/trigo e soja/trigo (PD12 M/T e PD12 S/T, respectivamente) e por 22 anos (PD22 M/T e PD22 S/T, respectivamente). As emissões de CO2 do solo foram aproximadamente 20 % mais elevadas no PD22 em relação ao PD12. As emissões de CO2 apresentaram correlação significativa (R² = 0,85; p < 0,05) com a temperatura do solo, com emissões médias 40 % menores, registradas nos meses com temperaturas mais baixas. As emissões mais elevadas de N2O foram observadas após a colheita das culturas de verão, sobretudo na sucessão milho/trigo, em relação à sucessão soja/trigo. As emissões de N2O foram aproximadamente 25 % maiores após aplicação do fertilizante nitrogenado na cultura do trigo nas duas sucessões e apresentaram correlação significativa (R² = 0,88; p < 0,01) com o grau de saturação de água no solo (Sr %).

CO2, CH4 and N2O fluxes in an Ultisol treated with sewage sludge and cultivated with castor bean

Organic residue application into soil alter the emission of gases to atmosphere and CO2, CH4, N2O may contribute to increase the greenhouse effect. This experiment was carried out in a restoration area on a dystrophic Ultisol (PVAd) to quantify greenhouse gas (GHG) emissions from soil under castor bean cultivation, treated with sewage sludge (SS) or mineral fertilizer. The following treatments were tested: control without N; FertMin = mineral fertilizer; SS5 = 5 t ha-1 SS (37.5 kg ha-1 N); SS10 = 10 t ha-1 SS (75 kg ha-1 N); and SS20 = 20 t ha-1 SS (150 kg ha-1 N). The amount of sludge was based on the recommended rate of N for castor bean (75 kg ha-1), the N level of SS and the mineralization fraction of N from SS. Soil gas emission was measured for 21 days. Sewage sludge and mineral fertilizers altered the CO2, CH4 and N2O fluxes. Soil moisture had no effect on GHG emissions and the gas fluxes was statistically equivalent after the application of FertMin and of 5 t ha-1 SS. The application of the entire crop N requirement in the form of SS practically doubled the Global Warming Potential (GWP) and the C equivalent emissions in comparison with FertMin treatments.

N2O emissions from a cultivated mollisol: optimal time of day for sampling and the role of soil temperature

The correct use of closed field chambers to determine N2O emissions requires defining the time of day that best represents the daily mean N2O flux. A short-term field experiment was carried out on a Mollisol soil, on which annual crops were grown under no-till management in the Pampa Ondulada of Argentina. The N2O emission rates were measured every 3 h for three consecutive days. Fluxes ranged from 62.58 to 145.99 ∝g N-N2O m-2 h-1 (average of five field chambers) and were negatively related (R² = 0.34, p < 0.01) to topsoil temperature (14 - 20 ºC). N2O emission rates measured between 9:00 and 12:00 am presented a high relationship to daily mean N2O flux (R² = 0.87, p < 0.01), showing that, in the study region, sampling in the mornings is preferable for GHG.